CN116759593A - Ru-M bimetallic monoatomic catalyst and preparation method and application thereof - Google Patents
Ru-M bimetallic monoatomic catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000000446 fuel Substances 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 10
- 150000003303 ruthenium Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- 102000020897 Formins Human genes 0.000 claims description 2
- 108091022623 Formins Proteins 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical group [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000002739 metals Chemical class 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000010411 electrocatalyst Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 22
- 125000004429 atom Chemical group 0.000 description 17
- 238000010586 diagram Methods 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000004075 alteration Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001815 facial effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 230000005469 synchrotron radiation Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019854 Ru—N Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A Ru-M bimetallic monoatomic catalyst and a preparation method and application thereof relate to an electrocatalyst and a preparation method and application thereof. The method aims to solve the technical problem that the oxygen reduction performance of the existing transition metal single-atom doped M-N-C catalyst is relatively poor. The catalyst of the invention is: atoms of two metals of Ru and M form an atom pair and are embedded into a carbon carrier, wherein Ru and M are respectively coordinated with 4N, and Ru and M share two N and represent an N-bridged Ru=2N=M coordination structure; wherein M is Cr, mn, fe or Co. The preparation method comprises the following steps: 1. preparing a Ru-ZIF-8 precursor; 2. preparation of Ru and N Co-alloysA doped porous carbon support; 3. Ru-M bimetallic monoatomic catalyst is prepared. The catalyst can be used in the fields of proton exchange membrane fuel cells and metal air cells, and particularly has a peak power density breakthrough of 1W/cm in proton exchange membrane fuel cells 2 。
Description
Technical Field
The invention belongs to the field of preparation and application of electrocatalysts, and particularly relates to a Ru-M bimetallic monoatomic catalyst and a preparation method and application thereof.
Background
With the rapid development of world economy and the continuous growth of global population, the global energy shortage problem, the environmental pollution problem and the climate warming problem caused by the greenhouse effect are increasingly severe, so that the development of new energy technologies is urgently needed. Proton exchange membrane fuel cells and metal air cells are considered clean new energy storage and conversion devices. The kinetics of the cathodic oxygen reduction reaction, which is the core step thereof, are very slow, requiring a noble metal Pt/C catalyst. However, pt resources are short, cost is high, stability is poor, and thus development of a Pt-free based catalyst having high activity and high stability is urgently required. In recent years, transition metal doped M-N-C catalysts have demonstrated excellent oxygen reduction performance, especially Fe-N-C catalysts. However, further improvement of oxygen reduction performance is limited due to the single reaction site of the single-atom catalyst and the single adsorption mode of the oxygen reduction reaction intermediate. Furthermore, on monoatomic sites, oxygen tends to adsorb in Pauling mode, which makes the cleavage of O-O bonds more difficult.
Disclosure of Invention
The invention aims to solve the technical problem that the oxygen reduction performance of the existing transition metal single-atom doped M-N-C catalyst is relatively poor, and provides a Ru-M bimetallic single-atom catalyst and a preparation method and application thereof. The Ru-M bimetallic monoatomic catalyst has high activity and high stability, and can be applied to cathode oxygen reduction electrocatalytic materials in the new energy fields of proton exchange membrane fuel cells, metal air cells and the like.
The Ru-M bimetallic monoatomic catalyst of the invention is: atoms of two metals of Ru and M form an atom pair and are embedded into a carbon carrier, wherein Ru and M are respectively coordinated with 4N, and Ru and M share two N and represent an N-bridged Ru=2N=M coordination structure; ru and MThe distance between the atoms isThe M metal is Cr, mn, fe or Co. The catalyst was designated Ru-M-NC.
Further, in the Ru-M bimetallic monoatomic catalyst, the mol ratio of Ru to M is 1:0.7 to 1.3.
Furthermore, in the Ru-M bimetallic monoatomic catalyst, the mass of Ru and M accounts for 0.5-1.5% of the mass of the whole catalyst.
The preparation method of the Ru-M bimetallic monoatomic catalyst comprises the following steps:
1. preparation of Ru-ZIF-8 (zeolite imidazole skeleton porous crystal material) precursor: firstly, uniformly dissolving 2-methylimidazole in a methanol solution to obtain a solution I; then zinc nitrate and soluble ruthenium salt are dissolved in a mixed solution of methanol and ethanol to obtain a solution II; pouring the solution II into the solution I, vigorously stirring at 90-120 r/min for 20-24 h at room temperature, and then centrifuging, washing and drying to obtain a Ru-ZIF-8 precursor;
2. preparation of Ru and N co-doped porous carbon support: uniformly grinding a Ru-ZIF-8 precursor, placing the Ru-ZIF-8 precursor into a tube furnace, performing high-temperature heat treatment in a reducing atmosphere, and naturally cooling to obtain a Ru and N co-doped carbon carrier; recorded as Ru-NC;
3. preparation of Ru-M bimetallic monoatomic catalyst: dissolving bipyridine and M metal salt in a mixed solution of ethanol and water, and uniformly stirring to obtain a solution III; the M metal salt is soluble Cr salt, mn salt, fe salt or Co salt; uniformly dispersing Ru and N co-doped carbon carrier in a solution III, stirring for 5-10 min at room temperature, and then carrying out ultrasonic treatment for 1-3 h; suction filtering, washing with deionized water, filtering and drying; finally, placing the mixture in a tube furnace, performing second high-temperature heat treatment in an inert atmosphere, and naturally cooling to obtain the Ru-M bimetallic monoatomic catalyst, which is denoted as Ru-M-NC.
Further, the soluble ruthenium salt in the first step is ruthenium acetate, ruthenium chloride trihydrate or ruthenium acetylacetonate.
Further, the molar ratio of zinc nitrate to soluble ruthenium salt is (10-40): 1.
Further, the molar ratio of the 2-methylimidazole to the soluble ruthenium salt in the first step is (200-250): 1.
Further, the mixed solution of the methanol and the ethanol in the first step is formed by mixing (1-3) according to the volume ratio of the methanol to the ethanol. The soluble ruthenium salt is dissolved in the mixed solution of methanol and ethanol, which is helpful for the full dissolution of the soluble ruthenium salt.
Further, the centrifugal and washing rotational speed in the first step is 10000-12000r min -1 。
Further, the washing in the step one is performed 3 times by methanol, and the washing time is 10-30 min each time. The methanol solution washing can efficiently remove metal ions which are not coordinated and do not enter the Ru-ZIF-8 crystal structure.
Further, in the second step, the reducing atmosphere is H 2 Ar mixture gas, wherein H 2 The volume percentage content of (2) is 5-20%. H 2 The mixed gas of Ar and Zn can promote the volatilization and removal of coordination nodes and provide guarantee for the preparation of the porous carbon carrier.
Further, the bipyridine in the third step is 2,2' -bipyridine.
Further, the mixed solution of ethanol and water in the step three is formed by mixing (1-3) ethanol and water according to the volume ratio of 1. The bipyridine and the M metal salt are dissolved in the mixed solution of ethanol and water, which is favorable for the full dissolution and effective coordination of the bipyridine and the M metal salt.
Further, the ratio of the amount of Ru species in the Ru and N co-doped carbon support described in step three to the amount of M metal salt species is 1: (0.7-1.3).
Further, the inert atmosphere in the third step is Ar or N 2 。
Further, the heat treatment conditions in the second and third steps are as follows: the heat treatment temperature is 900-1000 ℃, the heat treatment time is 0.5-2 h, the heating rate is 1-20 ℃ for min -1 All heat treatments require aeration at room temperatureHeating after 3-5 h; ventilation is carried out for 3-5 hours before heat treatment, so that the heat treatment process is carried out under corresponding gas, and the interference of oxygen in a pipeline is eliminated.
Further, the drying conditions in the first step and the third step are vacuum drying, the temperature is 60-80 ℃, and the drying time is 6-8 hours.
The Ru-M bimetallic monoatomic catalyst is applied to the cathode oxygen reduction reaction of a proton exchange membrane fuel cell or a metal air cell.
The Ru-M bimetallic monoatomic catalyst prepared by the invention can provide a new oxygen reduction reaction path, namely a dissociation path, because Ru and M are reactive active sites and the adsorption of Ru and M to oxygen species is stronger, O 2 Are more easily bridged on the Ru and M double active sites and undergo direct cleavage of O-O, the specific reaction paths are as follows:
(i)2*+O 2 +H + +e - →*O+*OH
(ii)*O+*OH+H + +e - →*OH+*OH
(iii)*OH+*OH+H + +e - →*OH+H 2 O
(iv)*OH+H + +e - →2*+H 2 O
the Ru-M bimetallic monoatomic catalyst provided by the invention comprises two adjacent active sites, ru and M bimetallic active centers are constructed, oxygen tends to be adsorbed in a bridge mode, so that direct fracture of O-O bonds is facilitated, and the synergistic effect and electronic regulation effect between the two active sites are facilitated, so that the limitation of monoatomic reaction is broken, and the vertex of a volcanic diagram is broken through.
In contrast, the invention has the advantages and beneficial effects compared with the prior art:
1. compared with the single-atom catalyst, the Ru-M-NC (M=Cr, mn, fe or Co) bimetallic single-atom catalyst can provide two active sites, and Ru and M sites with stronger adsorption strength on oxygen promote O 2 Bridge adsorption and direct cleavage of O-O bonds, leading to oxygen reduction reactions with direct four-electron reversalShould be routed so as to effectively increase the rate of the oxygen reduction reaction of the catalyst.
2. Compared with a monoatomic catalyst, the direct four-electron oxygen reduction reaction path reduces H 2 O 2 The yield reduces the oxidation corrosion of free radicals to the carbon carrier and improves the stability of the catalyst.
3. Through two-step high-temperature heat treatment, the carbon material has higher graphitization degree, enhances the corrosion resistance of the carbon carrier, thereby improving the stability of the catalyst under the working condition, and simultaneously the porous carbon material enhances the accessibility of active sites, thereby enhancing the O 2 And the like.
4. The Ru-M bimetallic monoatomic catalyst prepared by the invention shows higher half-wave potential in acidic and alkaline electrolyte.
The Ru-M bimetallic monoatomic catalyst has the structural characteristics of Ru and M bimetallic monoatomic, ru and M are oxygen reduction active sites, exist in an atom pair mode and have low content, the catalyst constructs Ru and M bimetallic active sites, promotes the direct fracture of O-O bonds, breaks through the inherent linear relation of an oxygen reduction reaction path, accelerates the kinetics of the oxygen reduction reaction process, and breaks through 1W/cm of peak power density in the fuel cell test 2 . Can be used in the fields of proton exchange membrane fuel cells and metal air cells.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention; in the figure, yellow pellets represent Ru metal atoms, orange pellets represent M metal atoms, gray pellets represent C atoms, blue pellets represent N atoms, and silver gray pellets represent Zn atoms;
FIG. 2 is a scanning electron microscope image of the Ru-ZIF-8 precursor prepared in step one of example 1;
FIG. 3 is a scanning electron microscope image of the Ru-NC porous carbon support prepared in step two of example 1;
FIG. 4 is an EDS facial scan of Ru-Fe-NC prepared in example 1;
FIG. 5 is XRD patterns of Ru-Fe-NC of example 1, fe-NC prepared by comparative example, NC and Ru-NC;
FIG. 6 is a schematic diagram showing the transmission diagram, the spherical aberration diagram, and the atomic pair distance measurement of Ru-Fe-NC prepared in example 1;
FIG. 7 is an EXAFS diagram of an Ru and Fe element synchrotron radiation X-ray absorbing structure of example 1;
FIG. 8 is a schematic diagram of the structure of Ru-Fe-NC prepared in example 1; in the figure, gray pellets represent C atoms, blue pellets represent N atoms, yellow pellets represent Ru atoms, and orange pellets represent Fe atoms;
FIG. 9 is a graph showing oxygen reduction properties of Ru-Fe-NC of example 1, fe-NC prepared by comparative example, and Ru-NC in 0.1M KOH;
FIG. 10 is a graph comparing the performance of Ru-Fe-NC of example 1, fe-NC prepared by comparative example, and Ru-NC with commercial Pt/C in fuel cell testing;
FIG. 11 is a transmission EDS facial scan image of Ru-Co-NC of example 2;
FIG. 12 is a schematic diagram of Ru-Co-NC spherical aberration diagram of example 2 and atomic pair distance measurement;
FIG. 13 is a graph showing oxygen reduction performance of Ru-Co-NC of example 2 in 0.1M KOH.
Detailed Description
The following description of the present invention refers to the accompanying drawings and examples, but is not limited to the same, and modifications and equivalents of the present invention can be made without departing from the spirit and scope of the present invention.
Example 1: the preparation method of the Ru-Fe bimetallic single-atom catalyst comprises the following steps:
1. preparation of Ru-ZIF-8 (zeolite imidazole skeleton porous crystal material) precursor: firstly, uniformly dissolving 7.2g of 2-methylimidazole in a methanol solution to obtain a solution I; then 3.3g of zinc nitrate and 75mg of ruthenium trichloride are dissolved in a mixed solution of methanol and ethanol to obtain a solution II, wherein the mixed solution of the methanol and the ethanol is prepared by the following steps of: 1, mixing the materials in proportion; pouring the solution II into the solution I rapidly, stirring vigorously at the stirring speed of 100r/min for 24 hours at room temperature, and then centrifuging, washing and drying to obtain a Ru-ZIF-8 precursor;
2. preparation of Ru and N co-doped porous carbon support: grinding Ru-ZIF-8 precursor uniformly, placing in a tube furnace, and introducing H at room temperature 2 Mixed gas with Ar, H in the mixed gas 2 After ventilation for 4 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, maintaining for 1 hour, carrying out high-temperature heat treatment under a reducing atmosphere, and naturally cooling to obtain the Ru and N co-doped carbon carrier; recorded as Ru-NC;
3. preparation of Ru-Fe bimetallic monoatomic catalyst: 200mg of 2,2' -bipyridine and 100mg of ferrous sulfate heptahydrate are dissolved in a mixed solution prepared by mixing 7.5mL of ethanol and 7.5mL of water, and the mixed solution is uniformly stirred to obtain a solution III; then uniformly dispersing 30mg of Ru and N co-doped carbon carrier in the solution III, stirring at room temperature for 10min, and then carrying out ultrasonic treatment for 1h; suction filtering, washing with deionized water, filtering and drying; finally, placing the mixture in a tube furnace, introducing Ar gas for 4 hours at room temperature, then raising the temperature to 950 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for 1 hour, performing second-time high-temperature heat treatment in the Ar gas in an inert atmosphere, and naturally cooling to obtain the Ru-Fe bimetallic monoatomic catalyst which is recorded as Ru-Fe-NC.
The scanning electron microscope photograph of the Ru-ZIF-8 precursor obtained in the first step of the embodiment is shown in FIG. 2, and as can be seen from FIG. 2, the particle size of the Ru-ZIF-8 precursor is 40-50 nm.
As shown in FIG. 3, the scanning electron microscope photograph of Ru-NC obtained in the second step of the present embodiment shows that the Ru-NC particles are dodecahedron and have uniform morphology from FIG. 3.
As can be seen from FIG. 4, the EDS facial scan of Ru-Fe-NC obtained in step three of the present example is shown in FIG. 4, and Ru, fe, N and C are uniformly distributed, and no metal nanoclusters and particles are present, indicating that Ru and Fe exist in an atomic dispersed form.
Comparative example 1: this example prepares Fe-NC for comparison, and the specific procedure is as follows:
1. preparation of ZIF-8 (zeolite imidazole ester skeleton structure porous crystal material) precursor: firstly, 7.2g of 2-methylimidazole is uniformly dissolved in methanol to obtain a solution I, 3.3g of zinc nitrate is dissolved in a mixed solution of methanol and ethanol to obtain a solution II, wherein the mixed solution of methanol and ethanol is prepared by mixing methanol and ethanol according to the volume ratio of 1:1, mixing the materials in proportion; pouring the solution II into the solution I rapidly, stirring vigorously at the stirring speed of 100r/min for 24 hours at room temperature, and centrifuging, washing and drying to obtain a ZIF-8 precursor;
2. preparation of N-doped porous carbon support: uniformly grinding ZIF-8 precursor, placing in a tube furnace, and introducing H at room temperature 2 Mixed gas with Ar, H in the mixed gas 2 After ventilation for 4 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, maintaining for 1 hour, performing high-temperature heat treatment in a reducing atmosphere, and naturally cooling to obtain an N-doped carbon carrier, which is denoted as NC;
3. preparation of Fe-NC monoatomic catalyst: 200mg of 2,2' -bipyridine and 100mg of ferrous sulfate heptahydrate are dissolved in a mixed solution formed by mixing 7.5mL of ethanol and 7.5mL of water, and the mixed solution is uniformly stirred to obtain a solution III; then uniformly dispersing 30mg of N-doped carbon carrier (NC) in the solution III, stirring for 10min at room temperature, and then carrying out ultrasonic treatment for 1h; filtering, washing with deionized water, and drying; and finally, placing the dried sample in a tube furnace, introducing Ar gas for 4 hours, heating to 950 ℃ at a heating rate of 5 ℃/min, maintaining for 1 hour, performing second-time high-temperature heat treatment in Ar gas in an inert atmosphere, and naturally cooling to obtain the Fe-NC monoatomic catalyst, which is marked as Fe-NC.
Comparative example 2: the comparative Ru-NC was prepared in this example as follows:
1. preparation of Ru-ZIF-8 (zeolite imidazole skeleton porous crystal material) precursor: firstly, 7.2g of 2-methylimidazole is uniformly dissolved in a methanol solution to obtain a solution I, 3.3g of zinc nitrate and 75mg of ruthenium trichloride are dissolved in a mixed solution of methanol and ethanol to obtain a solution II, wherein the mixed solution of the methanol and the ethanol is prepared by mixing the methanol and the ethanol according to the volume ratio of 1:1, mixing the materials in proportion; pouring the solution II into the solution I rapidly, stirring vigorously at 100r/min for 24 hours at room temperature, and then centrifuging, washing and drying to obtain a Ru-ZIF-8 precursor;
2. preparation of Ru and N co-doped porous carbon support: uniformly grinding the Ru-ZIF-8 precursor obtained in the step one, placing the ground Ru-ZIF-8 precursor into a tube furnace, and introducing H at room temperature 2 Mixed gas with Ar, H in the mixed gas 2 After ventilation for 4 hours, the temperature is raised to 950 ℃ at a heating rate of 5 ℃/min, the temperature is kept for 1 hour, the temperature is naturally reduced, and then the Ru and N co-doped carbon carrier is obtained and is recorded as Ru-NC.
XRD diffraction patterns of Ru-Fe-NC prepared in example 1, NC and Fe-NC prepared in comparative example 1, and Ru-NC prepared in comparative example 2 were tested, and the obtained XRD diffraction patterns are shown in FIG. 5, and it can be seen from FIG. 5 that only diffraction peaks of 002 crystal face and 101 crystal face of carbon appear in the patterns, and that no peaks of metal clusters or nanoparticles of Ru and Fe appear, indicating the existence form of atomic-scale dispersion of Ru and Fe. In FIG. 5, the metals in the three catalysts Ru-Fe-NC, ru-NC, and Fe-NC are all atomically dispersed, and no peak associated with metal particles or clusters, etc. appears. Because there is a sharp peak if there are metal particles or clusters, whereas current XRD has only a steamed bread peak with carbon, it is believed that there are no Ru or Fe related metal particles or clusters, demonstrating atomic scale dispersion of Ru and Fe.
The transmission diagram, the spherical aberration electron microscope diagram and the atomic pair distance measurement schematic diagram of Ru-Fe-NC prepared in example 1 are shown in FIG. 6, and the transmission diagram shows that no Ru and Fe nano particles and clusters exist, and meanwhile, the spherical aberration electron microscope diagram shows that a large number of Ru and Fe atom pairs exist, the brightness of two bright spots in the atom pairs is different, the brightness is related to the atomic number, the brightness of Ru is high, the brightness of Fe is low, and the distance between the two atoms is 0.246nm. In the preparation of Ru-Fe-NC in example 1, ru and M are added in two steps, ru is doped first, fe salt is adsorbed after heat treatment, and heat treatment is performed once. The two metal ions are introduced by twice high-temperature heat treatment, so that the active site density of the bimetallic single-atom catalyst can be controllably improved, alloy nano particles and clusters formed by two metals are prevented from being added simultaneously, and the graphitization degree of the catalyst can be further improved by twice high-temperature heat treatment, so that the stability of the catalyst is improved.
The EXAFS diagram of the Ru and Fe element synchrotron radiation X-ray absorption structure of Ru-Fe-NC prepared in example 1 is shown in FIG. 7, the left side is the K-side EXAFS spectrum K of Ru 2 Weighted fourier transform data, inThere is a distinct peak, mainly due to the coordination of the first shell Ru-N. No observation was made at->The peak is present, which indicates that Ru-Ru metal bond is not present in Ru-Fe-NC. At the same time->There is an additional small peak, which is affected by the adjacent Fe atoms. The right side is the K-edge EXAFS spectrum K of Fe 2 Weighted fourier transform data, in->There is a distinct peak, which is mainly due to the first shell Fe-N coordination. In addition, approximately->There is an extra small peak, different from +.> And->Due to adjacent Ru atoms. According to the extension edge fitting of the synchronous radiation EXAFS, determining that the coordination structure of Ru, fe and N is RuFeN6, the coordination number of Ru and N is 4, the coordination number of Fe and N is 4, the coordination number of Ru and Fe is 1, namely RuN4-FeN4, wherein Ru and Fe share two N, N bridged Ru=N2=Fe structures, and obtaining a structure model graph by combining the synchronous radiation and a data result of a spherical aberration electron microscope, such asFIG. 8 shows that in the drawings, gray represents a C atom, blue represents an N atom, yellow represents a Ru atom, orange represents a Fe atom, and the Ru-Fe-NC structure prepared by the present embodiment is more stable, and the structure adsorbs O 2 When O 2 The method is more prone to being carried out in a bridge adsorption mode, so that the direct fracture of O-O is accelerated, and the oxygen reduction reaction rate is improved.
Testing the electrochemical properties of Ru-Fe-NC prepared in example 1, fe-NC prepared in comparative example and Ru-NC in 0.1M KOH, using a three electrode test system, a glassy carbon electrode as the working electrode, ag/AgCl as the reference electrode, and Pt wire as the counter electrode, activating the Catalyst (CV) by cyclic voltammetry testing, followed by O 2 A Linear Sweep Voltammetry (LSV) test is carried out on saturated 0.1M KOH, the rotating speed is 900r, the voltage range is 1.10-0.00V (vs. RHE), the obtained polarization curve is shown in FIG. 9, and as can be seen from FIG. 9, the Ru-Fe-NC catalyst in 0.1M KOH has excellent performance, and the half-wave potential in an alkaline system is 0.926V, which is superior to that of monoatomic catalysts Ru-NC and Fe-NC.
The four catalysts of Ru-Fe-NC prepared in example 1, fe-NC prepared in comparative example, ru-NC, and commercial Pt/C were used in proton exchange membrane fuel cells to test catalyst performance. Preparing a membrane electrode by adopting a gas diffusion electrode method, firstly loading a commercial Pt/C catalyst and Nafion ionomer on carbon paper 1 to obtain an anode gas diffusion electrode, wherein the loading of the Pt/C catalyst is 0.1mg cm -2 Subsequently, ru-Fe-NC catalyst and Nafion ionomer were supported on carbon paper 2 to obtain a cathode gas diffusion electrode, the Ru-Fe-NC catalyst loading was 3.5mg cm -2 Respectively placing cathode and anode gas diffusion electrodes on two sides of a proton exchange membrane for hot pressing to obtain membrane electrodes, and finally assembling the membrane electrodes, a gasket, a flow field plate, a current collecting plate and an end plate into a proton exchange membrane fuel cell unit for testing the performance of the fuel cell to obtain the anode-cathode hydrogen fuel cell unit in H 2 /O 2 The polarization curve and the power density under the condition are shown in FIG. 10, and it is understood from FIG. 10 that Ru-Fe-NC exhibits an ultra-high peak power density (H 2 /O 2 ：1.152W cm -2 ) Close to commercial Pt/C performance. The battery performance of the Ru-Fe-NC catalyst prepared in example 1 was very large relative to that of comparative examples 1 and 2Because the Ru-Fe-NC bimetallic monoatomic catalyst can provide two active sites of Ru-Fe, has stronger adsorption to oxygen and can promote O compared with monoatomic catalysts of Ru-NC and Fe-NC 2 The bridge adsorption and the direct cleavage of O-O bond, and the direct oxygen reduction reaction is conducted directly in a four-electron reaction path, so that the rate of the oxygen reduction reaction of the catalyst is effectively improved. In the Ru-NC and Fe-NC single metal catalysts, the performance of catalyzing the oxygen reduction reaction is not ideal because the reaction site is single.
Comparing the electrochemical oxygen reduction performance of Ru-Fe-NC and Ru-NC and Fe-NC, in 0.1M KOH, the half-wave potential of Ru-Fe-NC is higher than that of Ru-NC and Fe-NC, and in proton exchange membrane fuel cell test, the peak power density of a cell assembled by Ru-Fe-NC is also much higher than that of Ru-NC and Fe-NC. In addition, the H is the direct four-electron path of the Ru-Fe-NC bimetallic single-atom catalyst 2 O 2 Yield is lower than that of Ru-NC and Fe-N, thereby helping to weaken H 2 O 2 Corrosion of the carbon support improves the stability of the catalyst.
Proton exchange membrane fuel cell performance assembled with the Ru-Fe-NC catalyst of example 1 also exceeded the literature reported relevant bimetallic monoatomic catalysts, as shown in table 1.
TABLE 1 comparison of performance of Ru-Fe-NC and proton exchange Membrane Fuel cells assembled with other catalysts
Example 2: this example differs from example 1 in that 100mg of ferrous sulfate heptahydrate in step three was replaced with 100mg of cobalt nitrate, and the other steps and parameters were the same as in example 1 to obtain a Ru-Co bimetallic monoatomic catalyst, designated Ru-Co-NC.
The transmitted EDS facial scan of Ru-Co-NC obtained in this example 2 is shown in FIG. 11, and it can be seen from FIG. 11 that there are no Ru and Co nanoparticles and clusters, ru, co, N and C are uniformly distributed, and no metallic nanoclusters and particles are present, indicating that Ru and Co are present in an atomic dispersed form.
The spherical aberration electron microscope image and the atomic pair distance measurement schematic diagram of Ru-Co-NC obtained in this example 2 are shown in FIG. 12, and it can be seen from FIG. 12 that there are a large number of Ru and Co atomic pairs, the two bright spots in the atomic pair have different brightnesses, the brightness is related to the atomic number, the brightness of Ru is high, the brightness of Co is low, and the distance between the two atoms is 0.239nm.
Testing the electrochemical properties of Ru-Co-NC obtained in this example 2, using a three electrode test system with a glassy carbon electrode as the working electrode, ag/AgCl as the reference electrode, and Pt wire as the counter electrode, activating the Catalyst (CV) by cyclic voltammetry testing, followed by O 2 The saturated 0.1M KOH was subjected to a Linear Sweep Voltammetry (LSV) test at a rotation speed of 900r and a voltage range of 1.10-0.00V (vs. RHE), and the resulting polarization curve is shown in FIG. 13. As can be seen from FIG. 13, ru-Co-NC also shows excellent oxygen reduction performance in 0.1M KOH, and its half-wave potential reaches 0.905V.
Claims (10)
1. The Ru-M bimetallic monoatomic catalyst is characterized in that the catalyst is formed by forming atom pairs of Ru and M atoms and embedding the atoms into a carbon carrier, wherein Ru and M are respectively coordinated with 4N, and Ru and M share two N and represent an N-bridged Ru=2N=M coordination structure; the distance between the two atoms Ru and M isThe M metal is Cr, mn, fe or Co.
2. The Ru-M bimetallic monoatomic catalyst of claim 1, wherein the Ru-M bimetallic monoatomic catalyst has a Ru to M molar ratio of 1: (0.7-1.3).
3. A Ru-M bimetallic monoatomic catalyst according to claim 1 or 2, characterised in that in the Ru-M bimetallic monoatomic catalyst, the mass of both Ru and M is between 0.5% and 1.5% of the mass of the whole catalyst.
4. A process for preparing a Ru-M bimetallic monoatomic catalyst as claimed in claim 1, characterised in that it is carried out according to the following steps:
1. preparation of Ru-ZIF-8 precursor: firstly, uniformly dissolving 2-methylimidazole in a methanol solution to obtain a solution I; then zinc nitrate and soluble ruthenium salt are dissolved in a mixed solution of methanol and ethanol to obtain a solution II; pouring the solution II into the solution I, vigorously stirring at 90-120 r/min for 20-24 h at room temperature, and then centrifuging, washing and drying to obtain a Ru-ZIF-8 precursor;
2. preparation of Ru and N co-doped porous carbon support: uniformly grinding a Ru-ZIF-8 precursor, placing the Ru-ZIF-8 precursor into a tube furnace, performing high-temperature heat treatment in a reducing atmosphere, and naturally cooling to obtain a Ru and N co-doped carbon carrier; recorded as Ru-NC;
3. preparation of Ru-M bimetallic monoatomic catalyst: dissolving bipyridine and M metal salt in a mixed solution of ethanol and water, and uniformly stirring to obtain a solution III; wherein the M metal salt is soluble Cr salt, mn salt, fe salt or Co salt; uniformly dispersing Ru and N co-doped carbon carrier in a solution III, stirring for 5-10 min at room temperature, and then carrying out ultrasonic treatment for 1-3 h; suction filtering, washing with deionized water, filtering and drying; and finally, placing the mixture in a tube furnace, performing second high-temperature heat treatment in an inert atmosphere, and naturally cooling to obtain the Ru-M bimetallic monoatomic catalyst.
5. The method for preparing a Ru-M bimetallic monoatomic catalyst according to claim 4, wherein the soluble ruthenium salt in the step one is ruthenium acetate, ruthenium chloride trihydrate or ruthenium acetylacetonate.
6. The method for preparing a Ru-M bimetallic monoatomic catalyst according to claim 4 or 5, wherein the molar ratio of zinc nitrate to soluble ruthenium salt in the step one is (10-40): 1.
7. A process for preparing a Ru-M bimetallic monoatomic catalyst as claimed in claim 4 or 5Characterized in that in the second step, the reducing atmosphere is H 2 Ar mixture gas, wherein H 2 The volume percentage content of (2) is 5-20%.
8. The method for preparing a Ru-M bimetallic single-atom catalyst as claimed in claim 4 or 5, wherein the bipyridine in step three is 2,2' -bipyridine.
9. The method for preparing a Ru-M bimetallic monoatomic catalyst as claimed in claim 4 or 5, wherein the heat treatment conditions in step two and step three are as follows: the heat treatment temperature is 900-1000 ℃, the heat treatment time is 0.5-2 h, the heating rate is 1-20 ℃ for min -1 All heat treatments were preceded by aeration at room temperature for 3-5 hours.
10. The use of a Ru-M bimetallic monoatomic catalyst as claimed in claim 1, wherein the use is in the cathodic oxygen reduction of proton exchange membrane fuel cells or metal air cells.
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